Addition agents for mineral oil lubricants and compositions containing the same



Patented May 9, 1950 ADDITION AGENTS FOR MINERAL OIL LU- BRICANTS ANDCOMPOSITIONS CONTAIN- ING THE SAME Herschel G. Smith, Wallinzford, andTroy L. Cantrell, Lansdowne, Pm, and John G. Peters, Audubon, N. J.,asslgnors to Gulf Oil Corporation, Pittsburgh, Pa., a. corporation ofPennsylvania No Drawing.

12 Claims. 1

This invention relates to addition agents for mineral oil lubricants andcompositions containing the same, and more particularly it relates toaddition agents which confer improved pressure-carrying, bearingcorrosion-inhibiting and detergent properties on mineral oil lubricants.

In the lubrication of internal combustion engines of all types,particularly when severe operating conditions are encountered, plainmineral lubricating oils often prove unsatisfactory in service becauseof the attendant deposition on the engine surfaces, such as the cylinderwalls, pistons and rings, of varnish, gum, or sludge. These effects areparticularly serious in modern engines operating under severeconditions, such as Diesel engines and aviation, truck, and tankengines. The problem has become increasingly serious due to the trendtoward (1) higher efificiency, or higher power output per unit weightper engine, (2) reduction in the amount of oil employed in thelubricating system of the engine, and (3) other conditions which tend toaccelerate deteriorating influences on mineral lubricating oils.

Formation of so-called varnishes and sludges on engine surfaces is dueto oxidation or polymerization effects (or both) on the lubricatingoils, as well as to like effects on or from products of combustion ofthe fuels which find their way ,by leakage into the engine crankcase andother parts of the engine.

The presence of these substances is disadvantageous for many reasons. Inparticular, the oil and fuel oxidation products tend to increaseringsticking and production of deposits on piston surfaces and in fixedparts of the combustion cham ber. sludges are formed in the crankcase ofthe engine, and the rate of corrosion of bearing surfaces is increased,especially with bearing alloys of the types now in use.

Petroleum oils intended for use under the severe conditions describedare almost always compounded with a mixture of substances each intendedto counteract one or more of the undesirable effects noted. Thesesubstances, which fall into a wide variety of chemical classifications,are generally known as "improvement agents or addition agents. However,preparation of satisfactory compounded lubricants is a matter ofconsiderable difiiculty. Some of the agents are of low potency, that is,a rather large amount has to be added to achieve the desired result.Often two or more agents are more or less incompatible with each other;and since the addition agents heretofore employed usually have aApplication May 26, 1947, Serial No. 750,635

rather low solubility the difficultles of preparing a useful lubricantare enhanced.

It is also a frequent characteristic of prior art addition agents thatthey are extremely dark in color. When such dark-colored addition agentsare added in effective amounts to a highly refined light-colored mineraloil, they often impart such a degree of color to the oil as to renderthe oil unmarketable.

It is an object of this invention, therefore, to provide addition agentsfor mineral oil lubricants which serve the functions of (1) inhibitingthe corrosion of bearings, (2) acting as a loosening or suspending agent(detergent) to prevent ringsticking, varnishing or coating of themetallic surfaces of internal combustion engines, and (3) acting as asuspending or dispersing agent for dispersing very small particles ofdeterioration products or contaminating materials in the oil.

Another object of this invention is to provide an addition agent formineral oil lubricants which is readily soluble and extremelylightcolored, and which may be added to any lightcolored mineral oillubricant without materially affecting the color thereof.

It is a further object of this invention to provide an addition agentfor mineral oil lubricants which confers markedly improved extremepressure characteristics on such mineral oil lubricants.

In our copending application, Serial No. 729,672, filed February 19,1947, we have disclosed and claimed mineral oil lubricants containing asaddition agents (1) a reaction product of octyl phenol with a sulfurchloride and a relatively small amount of phosphorus sesquisulfide, and

(2) the condensation product of formaldehyde and a substantially neutralmetal salt of the aforesaid reaction product, the said metal being ametal of group II of the periodic table selected from the groupconsisting of magnesium, calcium, barium and zinc. We have now foundthat an excellent addition agent may be prepared by substitutingstannous tin for the aforesaid group II metals.

Accordingly, the objects of our invention are achieved by providingmineral oil lubricants containing as addition agents (1) a reactionprodnot of an octyl phenol with a sulfur chloride and a relatively smallamount of phosphorus sesquisulfide, and (2) the condensation product offormaldehyde and a substantially neutral stannous salt of the aforesaidreaction product. We consider such condensation products and the methodof preparing them novel, and as parts 3 of our invention. The reactionproducts of an octyl phenol with a sulfur chloride and a relativelysmall amount of phosphorus eesquisulilde, as well as the method ofpreparing such reaction products, are claimed in our aboveidentifiedcopending application.

We prepare the reaction product of an octyl phenol with a sulfurchloride and phosphorus sesquisulflde in accordance with our priorcopending application, Serial No. 729,672. In accordance therewith, wereact an octyl phenol with from 0.5 to 30 per cent by weight on theoctyl phenol of a sulfur chloride and from 0.1 to 5 per cent by weighton the octyl phenol of phosphorus sesquisulfide. The reaction may takeplace at room temperature, and it usually is preferred to initiate thereaction at such temperature and then raise the temperature to no higherthan 350 F. to complete the reaction;

However the reaction may take place at any temperature ranging from roomtemperature to 350 F., provided care is taken that the lattertemperature is not exceeded. If the temperature of 350 F. is exceeded toany great extent, especially in the initial stages of the reaction, thereaction product formed will tend to be dark-colored and insoluble inmineral oil lubricants. It is desirable to use a volatile solvent in thepreparation of the octyl phenol reaction product. A wide variety ofsolvents may be employed such as benzene, toluene, hexane, carbontetrachloride, chloroform, cyclohexane and others. The solvent should beinert in the reaction and for this reason materials containing reactivehydroxyl groups and the like, such as alcohols and the like, should notbe employed. Since the solvent is removed from the reaction productafter the reaction has been completed, it is desirable that the solventbe relatively volatile and therefore a solvent having a boiling pointabove 320 F. should not be used.

We may use any octyl phenol in the preparation of the reaction product.The octyl phenols may be prepared by any method known to the art, butthey are preferably made in accordance with the procedure shown in U. S.Patent No. 2,149,759. In accordance with the procedure of said patent,phenol is reacted with a mixture of isomeric octenes, such as isavailable at the refinery in commercial diisobutylene polymer, in thepresence of a condensing agent such as concentrated sulfuric acid. Theoctyl phenol prepared in this manner is a mixture of isomeric octylphenols, but it is believed to contain a preponderant amount oftetramethyl butyl phenol (para-iso-octyl phenol). However, our inventionis not limited to the use of any specific octyl phenol or to octylphenols derived from any specific source. Thus any one of the isomericoctyl phenols or mixtures thereof may be employed with good results inaccordance with our invention.

The sulfur chloride used in accordance with our invention is preferablysulfur monochloride. However, other sulfur chlorides such as sulfurdichloride and sulfur tetrachloride or mixtures thereof may be employed.When sulfur tetrachloride is employed alone, it is preferred to usesmaller proportions thereof within the range given because the largerproportions tend to produce products which are darker in color than whenthe other sulfur chlorides are employed. As previously stated, thesulfur chloride is reacted with the phenol in an amount 4 ranging from0.5 to 30 per cent by weight on the octyl phenol.

Example I.As an example of the preparation of the octyl phenol reactionproduct, 1374 pounds of an octyl phenol, 13 pounds of phosphorussesquisulfide (P483) and 1331 pounds of benzene were placed into areaction vessel equipped with an agitator, means for heating andcooling, and a reflux condenser. Then 270 pounds of sulfur monochloride(SaClz) were added slowly while keeping the reaction mixture at atemperature of 60 F. The addition of the sulfur monochloride requiredapproximately 4 hours. At this time the temperature was raised to 180 F.and the mixture was refluxed for 20 hours at this temperature in orderto complete the reaction. At the end of this time the benzene wasdistilled off and the residue was heated to 250 F. under a vacuum ofapproximately 15 inches of mercury in order to strip off all of thebenzene. The residue was then diluted with 1500 pounds of a mineral oilhaving the following properties:

Gravity, API 32.0 Viscosity, SUV: F 72.4 Flash, 00, F 345' Fire, 00, F395 Pour, F +20 Color, NPA 1.5 Carbon residue, per cent 0.01Neutralization No 0.02

' The solution of the octyl phenol reaction product in the mineral oilhad the following properties:

Gravity, API 17.3 Viscosity, SUV: 100 F 1103 Flash, 00, F 385 Fire, 00,"F 450 Pour, F +5 Color, NPA 2.50 Sulfur, per cent r 5132 The reactionproducts obtained from octyl phenol, a sulfur chloride and phosphorussesquisulflde are excellent addition agents for mineral oil lubricantcompositions. They are readily soluble in all types of mineral oils,that is, parafiinic, naphthenic or mixed base mineral oils, and can beblended with mineral oils in high proportions as is shown in thepreceding example. This excellent solubility of our new addition agentsenables the preparation of concentrated solutions thereof which may thenbe diluted down to the proportions desired in the final mineral oillubricant composition. As shown in our copending application, the octylphenol reaction products confer excellent pressure-carrying, bearingcorrosion-inhibiting and detergent properties on the mineral lubricatingoils with which they are incorporated. For these purposes our newaddition agents are generally added to mineral oils in minor amounts,say from 0.1 to 15 per cent by weight on the mineral oil. Ordinarilysmall amounts as low as 0.1 per cent by weight are suflicient to effectthe desired improvement. However, when extreme pressure properties areto be conferred on a mineral lubricating oil composition, it willordinarily be desirable to use higher amounts, as high as 15 per cent.

In accordance with the present invention, we have found that theproperties of mineral oil lubricating compositions containing the octylphenol reaction products described above may be condensation derivativeof the above described reaction product. More particularly, there isformed a substantially neutral stannous salt of the reaction product ofan octyl phenol with a sulfur chloride and phosphorus sesquisulfldeprepared in accordance with the preceding disclosure, and the resultingsalt is condensed with formaldehyde or a formaldehyde-yielding compound.When the resulting condensation derivative and the original reactionproduct are both added to a mineral oil lubricant composition, theproperties of the composition are still further improved, particularlyin regard to inhibiting bearing corrosion.

The formation of a substantially neutral stannous salt of the reactionproduct of an octyl phenol with a sulfur chloride and a phosphorussesquisulflde may be accomplished in any conventional manner known tothe art and preferably by heating of the reaction product and stannousoxide or hydroxide. formed by the double decomposition method; that is,by first forming an alkali metal salt by neutralization with an alkalimetal hydroxide, such as potassium or sodium hydroxide, and thenreplacing the sodium ion with stannous tin by reaction with awater-soluble stannous salt, such as stannous chloride.

The condensation of the substantially neutral stannous salt of the abovedisclosed reaction product with formaldehyde or a formaldehyde-yieldingcompound is accomplished by heating to a temperature not in excess of275 F. Useful formaldehyde-yielding compounds are trioxymethylene,paraformaldehyde and the like. The amount of formaldehyde used rangesfrom 0.5 to 2 mols per mol of octyl phenol used in making the reactionproduct of an octyl phenol with a sulfur chloride and phosphorussesquisulfide. Formaldehyde-yielding compounds are employed in amountsequivalent to the amount of formaldehyde yielded by such compoundswithin the range above stated. Following condensation with theformaldehyde or formaldehyde-yielding compound, the condensation productis dehydrated.

The following example illustrates the preparation of the condensationderivative of our invention.

Example II.--Thirteen hundred thirty one pounds of an octyl phenol, 65pounds of phosphorus sesquisulfide (P483) and 736 pounds of benzene wereplaced into a reaction vessel equipped with an agitator, means forheating and cooling, and a reflux condenser. Then 270 pounds of sulfurmonochloride (S2012) were added slowly while keeping the reactionmixture at a temperature of 60 F. The temperature was then raised to 180F. and the mixture was refluxed at this temperature for 20 hours. Thebenzene was then distilled off and the residue was heated to 280 F.under a vacuum of about inches of mercury. The resulting reactionproduct was then diluted with 1900 pounds of a mineral lubricating oilhaving the same properties as shown in Example I, and then 240 pounds ofsodium hydroxide were added in 30 per cent solution, and the mixtureheated to 210 F. for a period of 5 hours. Then 570 pounds of stannouschloride in water solution and 510 pounds of 37 per cent formaldehydesolution were added. The mixture was then heated with agitation at atemperature of 275 F. for 2 hours, distilling oil the water. The productThe salt may also be was then dried under a vacuum of 15 inches ofmercury and filtered through a continuous filter. The product obtainedhas the following properties:

The above described condensation derivative is also readily soluble inmineral lubricating oils, and as disclosed in Example II mayconveniently be prepared as a concentrate in mineral lubricating oils.When both the above described reaction product and the condensationderivative thereof are incorporated in a mineral oil lubricantcomposition as previously disclosed, minor amounts of both agents areordinarily sufficient to effect the desired improvement inpressure-carrying, bearing corrosion-inhibiting and detergentproperties. The total amount of both agents will generally range from0.1 to 15 per cent by weight on the mineral lubricating oil. Within thisrange, it is preferred to employ equal amounts by weight of the twoagents, but the proportions of the two agents with respect to each othermay vary from 10 to per cent by weight of the reaction product, and from90 to 10 per cent by weight of the condensation derivative.

The following table illustrates the improved mineral oil lubricantcompositions obtained by the use of our new addition agents. In thetable, composition A is a good grade uncompounded SAE 30 motor oil,composition B is composition A blended with 1 per cent by weight of thereaction product prepared in accordance with Example I, and compositionC is composition A blended with 1 per cent by weight of the reactionproduct prepared in accordance with Example I and 1 per cent by weightof the condensation derivative prepared in accordance with Example II.

A B C Gravity, API 29.3 29.0 28. 8 Viscosity, SUV

210 F 67. 5 67.1 66. 8 Viscosity Index- 104 103 102 Cloud, F none Pour,"F +5 5 +5 Aging Test, 32 F 24 Hrbright bright bright Room Temp. 15 daysbright bright bright Color, A l. 75 l. 75 2. 25 Appearance bright brightbright Sulfur, B, Per Cent 0.12 0. 19 0.17 Carbon Residue, Per Cent 0.110.13 0. 24 Precipitation No. nil nil Centrifuge Test, Separation, PerCent:

1500 R. P M., Room Temp, 2 Hrnil nil Neutralization No 0.02 0.02 0. 04Chevrolet 36 Hour Engine Test;

CBC Designation Engine Rating 75-541 9549 "29 Falex Wear Test:

1000 Lb. Gauge Load, 15 min.:

Wear: No. of Teeth falls 0 0 Gauge Load at Seizure, Lb 1, 100 1,000

As may be seen from the above data, the color 01. the base lubricatingoil remains unchanged and bright notwithstanding the addition of our newaddition agents. As shown by the data on the Falex Wear Test, even smallamounts of our new addition agents effectively improve thepressure-carrying properties of the base oil. When larger amounts areused the improvements obtained in pressure-carrying properties are evenmore striking. The remarkably effective detergent and bearing-corrosioninhibiting properties imparted to the base oil are shown by the data onthe Chevrolet 36 hour engine test. In the hyphenated figures shownthereunder, the figure to the left of the hyphen indicates the freedomfrom engine deposits expressed in per cent, the larger the per cent(approaching 100 as a limit) the cleaner the engine. The markedimprovement in detergent effects obtained from the use of our newaddition agents is clear. The figure to the right of the hyphenindicates the amount of bearing corrosion expressed in milligrams lossin weight of a standard bearing. As shown under composition B, a mineraloil lubricant composition containing the reaction product of an octylphenol with a sulfur chloride and phosphorus sesquisulfide reduces theloss in weight of the bearing from 541 milligrams to 49 milligrams. Asshown under composition C when the mineral oil lubricant compositioncontains both the aforesaid reaction product and the condensationderivative thereof, a still further improvement is obtained, the loss inweight of the bearing being only 29 milligrams. Our new addition agentsclearly confer excellent bearing corrosion-inhibiting properties.Finally, the above data show the excellent stability and solubility ofour new addition agents.

The Chevrolet 36 hour engine test referred to above is an acceptedstandard test designed to determine the oxidation and bearing corrosioncharacteristics of engine crank case oils designed for use under heavyduty service conditions. In this procedure, the crank case lubricant isevaluated with respect to its stability or resistance to oxidation,bearing corrosion and the deposition of contaminants resulting fromdecomposition and oxidation or other changes that occur in the lubricantin service. The procedure involves the intermittent operation of aspecial fi-cylinder automotive test engine at constant speed and loadfor a total of 36 hours subsequent to a run-in period of 8 hours atgraduated speeds and loads. Prior to each test a complete set of newpiston rings is installed and two new weighed copper-lead test bearingsare installed in symmetrical location. Performance of the test 011 isjudged by examination of the power section of the engine for depositsand by ascertaining the weight loss of the test bearings.

While we have shown in the examples the preparation of compoundedlubricating oils, our invention is not limited thereto, but comprisesall mineral oil lubricant compositions containing our new additionagents, such as greases and the like.

As used in the appended claims, the term formaldehyde includesformaldehyde-yielding compounds as well as formaldehyde itself.

What we claim is:

from 0.5 to 30 per cent by weight of the octyl phenol of a sulfurchloride and from 0.1 to 5 per cent by weight of the octyl phenol ofphosphorus sesquisulflde, neutralizing the reaction product with analkali metal hydroxide, reacting the neutralized reaction product with awater-soluble salt of stannous tin to form a substantially neutralstannous salt of the reaction product, condensing the substantiallyneutral stannous salt at an elevated temperature not exceeding 275 F.with from 0.5 to 2 mols of formaldehyde per mol of octyl phenol used inmaking said reaction product, and recovering the resulting condensationproduct.

3. An addition agent for mineral oil lubricants obtained by the processof claim 1.

4. The process of claim 2, wherein the watersoluble stannous salt isstannous chloride.

5. The process of preparing an addition agent for mineral oil lubricantswhich comprises simultaneously reacting at a temperature ranging fromroom temperature to 350 F. an octyl phenol with from 0.5 to 30 per centby weight of the octyl phenol of a sulfur chloride and from 0.1 to 5 percent by weight of the octyl phenol of phosphorus sesquisulfide,neutralizing the-reaction product obtained thereby with stannoushydroxide to obtain a substantially neutral reaction product, condensingthe neutral reaction product with formaldehyde by heating at atemperature not greater than 275 F. the neutralized reaction product andfrom 0.5 to 2 mols of formaldehyde permol of octyl phenol used in makingsaid reaction product.

6. The process of claim 5, wherein the octyl phenol, sulfur chloride andphosphorus sesquisulfide are reacted in the presence of a volatilesolvent, and the volatile solvent is distilled of! prior to neutralizingthe reaction product with stannous hydroxide.

7. The process of preparing an addition agent for mineral oil lubricantswhich comprises simultaneously reacting at a temperature ranging fromroom temperature to 350 F. and in the presence of a volatile solventhaving a maximum boiling point of 320 F. an octyl phenol with from 0.5to 30 per cent by weight of the octyl phenol of sulfur monochloride andfrom 0.1 to 5 per cent by weight of the octyl phenol of phosphorussesquisulfide, distilling off the solvent, diluting the residue with amineral lubricating oil, neutralizing the diluted residue with stannoushydroxide to obtain a substantially neutral reaction product, condensingthe neutral reaction product with formaldehyde by heating at atemperature not greater than 275 F. the neutralized reaction 1. Theprocess of preparing an addition agent for mineral oil lubricants whichcomprises simultaneously reacting at a temperature ranging from roomtemperature to 350 F. an octyl phenol with from 0.5 to 30 per cent byweight of the octyl phenol of a sulfur chloride and from 0.1 to 5 percent by weight of the octyl phenol of phosphorus sesquisulfide, forminga neutral stannous salt of the reaction product, and con densing theneutral stannous salt at an elevated temperature not exceeding 275 F.with from 0.5 to 2 mols of formaldehyde per mol of octyl phenol used inmaking said react on product.

2. The process of preparing an addition agent for mineral oil lubricantswhich comprises simultaneously reacting at a temperature ranging fromroom temperature to 350 F. an octyl phenol with product and from 0.5 to2 mols of formaldehyde per mol of octyl phenol used in making saidreaction product, dehydrating the resulting condensation product, andrecovering a solution of the dehydrated condensation product in amineral lubricating oil.

8. An addition agent for mineral oil lubricants .carrying, bearingcorrosion-inhibiting and detergent propcrties on the composition of (1)the simultaneous reaction product formed at a tem perature ranging fromroom temperature to 350 F. of an octyl phenol with from 0.5 to 30 percent by weight of the octyl phenol of a sulfur chloride and from 0.1 toper cent by weight of the octyl phenol of phosphorus sesquisulfide, and(2) the condensation product formed at an elevated temperature notexceeding 275 F. of formaldehyde and a substantially neutral stannoussalt of (1), the amount of formaldehyde being from 0.5 to 2 mols per molof octyl phenol employed to form (1), and the amounts of (1) and withrespectto each other ranging from to 90 per cent by weight of (1) andfrom 90 to 10 per cent by weight of (2) 11. A lubricant compositioncomprising a major amount of a mineral lubricating oil and a minoramount, from 0.1 to per cent by weight on the oil of: (1) thesimultaneous reaction product of an octyl phenol with from 0.5 to percent by weight of the octyl phenol of sulfur monochloride and from 0.1to 5 per cent by weight of the octyl phenol of phosphorus sesqulsulfide,said reaction product having been prepared at a temperature ranging fromroom temperature to 350 F. and in the presence of a volatile solventwhich is substantially distilled off; and (2) the anhydrous condensationproduct formed at an elevated temperature not exceeding 275 F. offormaldehyde and a substantially neutral stannous salt, the

amount of formaldehyde being from 0.5 to 2 mols per mol of octyi phenolemployed to form (1); and the amounts of (1) and (2) with respect toeach other ranging from 10 to per cent by weight of (1) and from 90 to10 per cent by weight of (2), and totaling from 0.1 to 15 per cent byweight on the mineral oil lubricating composition.

12. A lubricating composition in accordance with claim 11, wherein theamounts of (1) and (2) are equal.

HERSCHEL G. SMITH. TROY L. CANTRELL. JOHN G. PETERS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,301,002 Zerwick Nov. 3, 19422,362,624 Gaynor et a1 Nov. 14, 1944 2,409,687 Rogers et al Oct. 22,1946 2,415,833 Mikeska et a1 Feb. 18, 194'? 2,438,875 Reifl' Mar. 30,1948

1. THE PROCESS OF PREPARING AN ADDITION AGENT FOR MINERAL OIL LUBRICANTSWHICH COMPRISES SIMULTANEOUSLY REACTING AT A TEMPERATURE RANGING FROMROOM TEMPERATURE TO 350*F. AN OCTYL PHENOL WITH FROM 0.5 TO 30 PER CENTBY WEIGHT OF THE OCTYL PHENOL OF A SULFUR CHLORIDE AND FROM 0.1 TO 5 PERCENT BY WEIGHT OF THE OCTYL PHENOL OF PHOSPHORUS SESQUISULFIDE, FORMINGA NEUTRAL STANNOUS SALT OF THE REACTION PRODUCT, AND CONDENSING THENEUTRAL STANNOUS SALT AT AN ELEVATED TEMPERATURE NOT EXCEEDING 275*F.WITH FROM 0.5 TO 2 MOLS OF FORMALDEHYDE PER MOL OF OCTYL PHENOL USED INMAKING SAID REACTION PRODUCT.
 10. A LUBRICANT COMPOSITION COMPRISING AMAJOR AMOUNT OF A MINERAL LUBRICATING OIL AND MINOR AMOUNTS, SUFFICIENTTO CONFER IMPROVED PRESSURECARRYING, BEARING CORROSION-INHIBITING ANDDETERGENT PROPERTIES ON THE COMPOSITION OF (1) THE SIMULTANEOUS REACTIONPRODUCT FORMED AT A TEMPERATURE RANGING FROM ROOM TEMPERATURE TO 350*F.OF AN OCTYL PHENOL WITH FROM 0.5 TO 30 PER CENT BY WEIGHT OF THE OCTYLPHENOL OF A SULFUR CHLORIDE AND FROM 0.1 TO 5 PER CENT BY WEIGHT OF THEOCTYL PHENOL OF PHOSPHORUS SESQUISULFIDE, AND (2) THE CONDENSATIONPRODUCT FORMED AT AN ELEVATED TEMPERATURE NOT EXCEEDING 275*F. OFFORMALDEHYDE AND A SUBSTANTIALLY NEUTRAL STANNOUS SALT OF (1), THEAMOUNT OF FORMALDEHYDE BEING FROM 0.5 TO 2 MOLS PER MOL OF OCTYL PHENOLEMPLOYED TO FORM (1), AND THE AMOUNTS OF (1) AND (2) WITH RESPECT TOEACH OTHER RANGING FROM 10 TO 90 PER CENT BY WEIGHT OF (1) AND FROM 90TO 10 PER CENT BY WEIGHT OF (2).